Multistereocenter-containing cyclopentanoids from Ynamides via oxazolidinone-controlled nazarov cyclization

Manchala, Narasimhulu, Law, Hanson Y. L., Kerr, Daniel J., Volpe, Rohan, Lepage, Romain J., White, Jonathan M., Krenske, Elizabeth H. and Flynn, Bernard L. (2017) Multistereocenter-containing cyclopentanoids from Ynamides via oxazolidinone-controlled nazarov cyclization. Journal of Organic Chemistry, 82 13: 6511-6527. doi:10.1021/acs.joc.7b00082


Author Manchala, Narasimhulu
Law, Hanson Y. L.
Kerr, Daniel J.
Volpe, Rohan
Lepage, Romain J.
White, Jonathan M.
Krenske, Elizabeth H.
Flynn, Bernard L.
Title Multistereocenter-containing cyclopentanoids from Ynamides via oxazolidinone-controlled nazarov cyclization
Journal name Journal of Organic Chemistry   Check publisher's open access policy
ISSN 1520-6904
0022-3263
Publication date 2017-07-01
Year available 2017
Sub-type Article (original research)
DOI 10.1021/acs.joc.7b00082
Open Access Status Not yet assessed
Volume 82
Issue 13
Start page 6511
End page 6527
Total pages 17
Place of publication Washington, DC, United States
Publisher American Chemical Society
Language eng
Subject 1605 Organic Chemistry
Abstract Achieving ready-enantioselective access to multistereocenter-containing cyclopentyl rings is an area of great significance to organic synthesis. In this work, we describe a general protocol for accessing multistereocenter-containing cyclopentanoids from simple N-alkynyloxazolidinones (Ox-ynamides). This protocol involves conversion of Ox-ynamides into Ox-activated divinyl and aryl vinyl ketones that undergo facile Nazarov cyclization with excellent chemo-, regio-, and stereocontrol. The Ox auxiliary directs all aspects of reactivity and selectivity, both in the electrocyclization and in the subsequent transformations of the resulting oxyallyl intermediate. Stereoinduction in the electrocyclization results from a "coupled-torque" mechanism in which rotation of the Ox group, driven by increasing orbital overlap of the nitrogen lone pair with the incipient oxyallyl cation, is coupled with the rotation of the termini of the pentadienyl cation, favoring a particular direction of conrotatory ring closure (torquoselectivity). The associated lone-pair stabilization of the transition state by Ox promotes cyclization of traditionally resistant substrates, broadening the scope of this asymmetric Nazarov cyclization. The Ox group also facilitates the stereo- and regioselective incorporation of nucleophiles (Nu) and dienes, giving more complex, multistereocenter containing cyclopentanoids. Finally, the Ox group is readily removed and recovered or can be converted into other amine functionalities.
Keyword Chemistry, Organic
Chemistry
Q-Index Code C1
Q-Index Status Provisional Code
Grant ID DP150103131
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: HERDC Pre-Audit
School of Chemistry and Molecular Biosciences
 
Versions
Version Filter Type
Citation counts: TR Web of Science Citation Count  Cited 0 times in Thomson Reuters Web of Science Article
Scopus Citation Count Cited 0 times in Scopus Article
Google Scholar Search Google Scholar
Created: Sun, 30 Jul 2017, 01:00:44 EST by System User on behalf of Learning and Research Services (UQ Library)